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Publication numberUS3929622 A
Publication typeGrant
Publication dateDec 30, 1975
Filing dateSep 9, 1974
Priority dateSep 22, 1972
Publication numberUS 3929622 A, US 3929622A, US-A-3929622, US3929622 A, US3929622A
InventorsWilliam T Granquist
Original AssigneeNl Industries Inc
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Hydrocarbon cracking utilizing laminar heavy metal aluminosilicates
US 3929622 A
Abstract
Laminar 2 : 1 layer-lattice aluminosilicate minerals containing intra-lattice multivalent ions such as nickel, copper, cobalt and others. The minerals are particularly useful in catalytic operations. Procedures for preparing the inventive minerals are given.
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United States atent 1191 Granquist Dec. 30, 1975 [54] HYDROCARBON CRACKING UTILIZING 3,252,889 5/1966 Capell et al 208/120 M N HEAVY METAL 3,803,026 4/1974 .Iaffe 208/111 3,804,741 4/1974 Robson 208/110 ALUMINOSIUCATES 3,838,041 9 1974 Sawyer et a1. 208/120 [75] Inventor: William T. Granquist, Houston,

Tex. Primary ExaminerDelbert E. Gantz [73] Ass1gnee: N.L. Industries, Inc., New York, Assistant Examiner s h i Attorney, Agent, or FirmDelmar H. Larsen; Roy F. [22] Filed; Sept 9 1974 House; Robert L. Lehman [21] Appl. No.: 504,679

Related U.S. Application Data 57 ABSTRACT [62] Division of Ser. No. 291,252, Sept. 22, 1972, Pat.

,405. Laminar 2 l layer-lattice aluminosilicate minerals containing intra-lattice multivalent ions such as nickel, [52] US. Cl. 208/120; 252/455 Z copper, cobalt and others. The minerals are particu- [51 Int. Cl. C10G 11/04; B01J 29/28 larly useful in catalytic operations. Procedures for pre- [58] Field of Search 208/120 paring the inventive minerals are given.

[ 1 References Cited 5 Claims, 1 Drawing Figure UNITED STATES PATENTS 1,759,919 5/1930 Singer 423/328 o (tr/0czf)=//?w) .200- Q X A g 600-- \8 Q Q 5550 d'O/l/PO/T/OA/ m G 15 46- El Z=/-0 A X=/.5

3w /V/ 56 0/1/17- CZA (414-246;)

HYDROCARBON CRACKING UTILIZING LAMINAR HEAVY METAL ALUMINOSILICATES RELATED APPLICATION This application is a division of co-pending application Ser. No. 291,252, filed Sept. 22, 1972, now U.S. Pat. No. 3,852,405, issued Dec. 3, 1974.

INTRODUCTION This invention relates to nickel aluminosilicates, and more particularly to a novel group of mixed layer laminar heavy metal aluminosilicates and to their employment in catalytic reactions.

Compounds of alumina and silica of the most diverse types not only occur in nature but have been variously compounded and synthesized, and have been found to have varying degrees of catalytic activity for such reactions as hydrocarbon cracking, hydrocarbon reforming, various organic syntheses and conversions, and the like. The make-up of this very broad class of substances varies not only with respect to composition, but with respect to crystallinity, and encompasses such members as relatively amorphous silica-alumina cracking catalysts, relatively well crystallized acid-activated clays, highly crystalline zeolite minerals, both natural and synthesized, and others. A particular type furnishing a background for the present invention is that described in U.S. Pat. No. 3,252,757, issued May 24, 1966, and describing a mixed layer laminar silicate mineral, which has been found to have utility as a catalyst for many kinds of catalytic reactions.

Because of the very broad range of possible substances derived primarily from alumina and silica, it is not surprising that research in this broad field over nearly a century continues to yield novel types with, in some cases, surprising and unexpected properties, with suitability for particular reactions not shared by other members of the broad group.

An object of the present invention is to provide a novel group of heavy metal aluminosilicates and processes for making them.

Another object of the invention is to provide a novel group of aluminosilicates catalysts, having useful catalytic characteristics.

Other objects of the invention will become apparent as the description thereof proceeds.

Generally speaking and in accordance with illustrative embodiments of my invention, 1 provide a laminar, 2:1 layer-lattice aluminosilicate mineral containing varying degrees of substitution in both six-fold and four-fold coordinated structural sites and corresponding to the following overall formula for a given preparation:

2 ses3 0.01 sws2 0.02 5ew54 0.05 x 52.0

and where G is at least 08 mol fraction aluminum ion, the remainder consisting of trivalent metal cations having an ionic radius not to exceed 0.75 A;

Y is selected from the class consisting of divalent metallic ions having an ionic radius not to exceed 0.75 A and mixtures thereof;

Q is at least 0.95 mol fraction silicon ions, the remainder consisting of tetravalent ions having an ionic radius not to exceed 0.64 A;

R is selected from the group consisting of trivalent ions having an ionic radius not to exceed 0.64 A and mixtures thereof, and

C is at least one charge-balancing cation, with y being its valence and d being the number of such cations C where:

In the above statement of the nature of G, Y, Q, and R, it will be noted that those substituents other than aluminum and silicon are designated in terms of ionic radius and ionic charge. It is further clear from the formulation given that G, while consisting predominantly of aluminum ions, may include a minor proportion of trivalent ions isomorphously substituted for some of the aluminum ions without affecting the overall charge; and that Y consists of divalent metallic ions either isomorphously substituted for a like number of aluminum ions, whereby a charge dificit results, or substituted on the basis of three divalent ions for two aluminum trivalent ions with no resulting charge deficit, or a mixture of both. In like manner,-it is clear that Q, while consisting predominantly of silicon ions, may include a minor proportion of tetravalent ions isomorphously substituted for some of the silicon ions without affecting the overall charge; while R consists of trivalent ions isomorphously substituted for a like number of silicon ions, whereby a charge deficit results from the substitution of a trivalent ion for a tetravalent ion.

The specific elements which are included in the above formulation other than aluminum and silicon are relatively small in number, because of the limitations imposed by the stipulated ionic charge and ionic radius.

For the sake of convenience, a tabulation follows in which the elements usable in accordance with the invention are listed. It will be clear that this listing results from checking each element against its known valence states and its known ionic radius for each applicable valence state, taking into account the coordination number where the latter affects the ionic radius. Tables of ionic radius for various elements have appeared in the literature during the last half century, and in the case of disparity among the values given for a specified element, the best value has been chosen in the light of all of the known data, and this best value is the one which appears in the tables which follow.

G: Trivalent Maximum 0.75 A

Aluminum (Al) 0.50 Chromium (Cr) 0.64 Manganese (Mn) 0.62 Iron (Fe) 0.60 Cobalt (Co) 0.63 Gallium (Ga) 0.62 Rhodium (Rh) 0.68 Scandium (Sc) 0.73

Y: Divalent Maximum 0.75 A

G: Trivalent Maximum 0.75 A-continued R: Trivalent Maximum 0.64 A

Aluminum (Al) 0.50 Chromium (Cr) 0.64 Manganese (Mn) 0.62 Iron (Fe) 0.60 Cobalt (Co) 0.63 Gallium (Ga) 0.62

Returning now to the formulation given hereinabove, the first bracket represents the laminar layer-lattice unit cell formulation, which as was explained hereinabove possesses an inherent negative charge by reason of the fact that the positive charges of the cations are less than the negative charges of the anions. Since the inventive preparation as a whole is electrostatically neutral, the charge-balancing cations which are necessarily present are external to the lattice and are represented by the second bracket, in which C stands for the charge balancing cations taken as a whole, with y being their average charge and d being the number of chargebalancing cations per unit cell. It will be recognized that in this formulation, C may actually correspond to a large variety of charge-balancing cations simultaneously present, such as for example a mixture of hydrogen, sodium, calcium, and the like cations.

In accordance with a more particular formulation, the composition of the charge-balancing cations in the second bracket may conveniently be represented as wherein an bz dy =x 3(e2)w and M is selected from the group consisting of hydrogen, ammonium, alkali metal cations, multivalent metal cations other than aluminum, and partial hydroxides of multivalent metal cations, and n is the unsatisfied valence of M.

As will become apparent from the further description of my invention, this second, more particular characterization of the charge-balancing cations corresponds more closely to the products initially obtained in accordance with my preferred mode of preparation. Moreover, it provides explicitly for any hydroxyaluminum cations which may be present. It will be understood that such hydroxyaluminum cations are commonly present as a mixture of species, as described for example in US. Geological Survey Water-Supply Paper l827-A (1967), which is incorporated herein by reference. However, since these charge-balancing cations are essentially exchangeable without disturbing the lattice itself, the latter being represented by the first bracket, after having made a given preparation in accordance with the invention by a preferred procedure, it is relatively simple to exchange a portion or indeed substantially all of the cations in the second bracket for some other preselected cation or mixture of cations. Thus, for example, referring to the first general formulation given hereinabove, the chargebalancing cation C can at will be selected from such diverse species as lithium, rubidium, palladium, hydroxyaluminum, hydroxynickel, trimethylammonium, alkyl phosphonium, and the like cations and indeed mixtures thereof. Thus, C may be selected from the group consisting of alkali metal, alkaline earth metal, heavy metal, heavy metal partial hydroxide, ammonium, substituted ammonium,

substituted phosphonium, and the like cations and mixtures thereof.

Thoseskilled in the art will recognize, accordingly, that the first bracket of the above formula relates to a fixed array of ions in a tripartite lamina which for convenience may be described as muscovite-like, and in which the positive ions shown in the first parenthesis are in octahedral coordination with sheets comprising oxygen, hydroxyl, and fluoride ions; whereas the positive ions shown in the second parenthesis in the first bracket are in tetrahedral coordination jointly with the aforesaid sheets of oxygen, hydroxyl, and fluoride ions, and also with sheets of oxygen ions in essentially a hexagonal ring array, constituting the external faces of the tripartite lamina. The positive ions shown in the second bracket have no essentially fixed position, but are in effect external to the lattice of the tripartite lamina.

Those skilled in the art will also recognize that when some of the parameters in the above formulations have values outside of the stipulated ranges, the formulations reduce to representations of various end members of a broad group of laminar aluminosilicates, which of course are outside of the scope of the present invention. Thus, for example, when w and x both equal zero, and no fluoride ion is present, the first bracket describes the mineral pyrophyllite. From the first equation set forth under the formula, it will be seen that the factor d is equal to zero, sothat the ionic species set forth in the second bracket are not present, which of course results from the fact that the lattice of pyrophyllite is charge-balanced. Again,,for the case in which x equals zero, w equals two, 2 equals two, and no fluoride is present, a mineral results in which the lattice is likewise chargebalanced, and the ionic species set forth in the second bracket are not present. Such a mineral is described in US. Pat. No. 2,658,875, to Cornelis et al.

In general, 2:1 layer-lattice aluminosilicate minerals or in alternative nomenclature, tripartite aluminosilicate minerals of the type concerned in the present invention, may be classified as either dioctahedral or trioctahedral, depending upon whether the number of cations per unit cell in the octahedral (or inner) layer is approximately 4or 6 respectively. The foregoing structural formula is as stated an overall formula for a given preparation, and the fact that the number of such octahedral cations may vary from 4 to 6 in a continuous manner in the formulation given does not mean that, a single lamina is present having such an intermediate number of cations. in point of fact, the individual laminae are believed to be either dioctahedral or trioctahedral, and in a given preparation the relative proportions of the dioctahedral and trioctahedral species will give rise to the numerical values obtained in quantitatively characterizing the preparation in accordance with the foregoing formula. Where e in the formulation is intermediate between 2 and 3, accordingly, both 1:1 and 3:2 substitutions are present. Because of the extremely small particle size of the minerals in accordance with the invention, the exact physical nature of these mixed phase systems is uncertain. In any case, the products in accordance with the invention which are produced by simultaneously synthesizing both phases in place in a single reaction mixture to produce a mixed-phase mineral differ significantly from compositionally similar mixtures obtained by simply mixing together the separately synthesized dioctahedral and trioctahedral members.

It may be emphasized that each product made in accordance with the invention is a simple mineral species, even though it may contain two phases, because in the latter case the phases are believed to be interlaminated on a scale substantially that of the individual layer lattices. Any naturally occurring clay exhibiting this construction is generally referred to as a mixedlayer mineral.

The minerals in accordance with the invention are synthesized by a hydrothermal route, detailed examples of which will be given later. It will be observed that all such examples show the synthesis taking place in a heated aqueous mixture, as indeed is understood by those skilled in the art by the term hydrothermal synthesis." The procedure follows in a general way that set forth in the aforementioned U.S. Pat. No. 3,252,757, except that the cited patent does not relate to the inventive aluminosilicates, which contain additional elements, so that the reaction mixtures required in the present invention are substantially different. As will be evident from the structural formula already given, the reaction mixture of the hydrothermal synthesis includes a source of one or more multivalent cations other than aluminum and silicon. For example, for the case of nickel, this may be a relatively soluble compound, such as for example, nickel acetate, nickel fluoride, nickel nitrate, and the like; or it may be a relatively insoluble nickel compound such as nickel hydroxide. It is of interest that in general the inclusion of soluble nickel salts in the reaction mixture tends to cause the nickel to occur predominantly in the trioctahedral phase, while relatively insoluble nickel compounds promote its occurence in the dioctahedral phase. The terms are well understood in the art, and a brief explanation in addition to that already given may be found on page 156 of the book by George Brown The X-Ray Identification and Crystal Structures of Clay Minerals, London 1961. The classical paper by Ross and Hendricks Minerals of the Montmorillonite Group, U.S. Geological Survey Professional Paper 205-B (1945) is helpful, particularly for its treatment of variation of the members of a given series of laminar aluminosilicate minerals.

For the other elements useful in practising the invention, such as cobalt, gallium, copper, zinc, iron, manganese, and so forth, as more fully listed hereinabove, the most commonly available simple inorganic and organic compounds thereof may in general be used, as will be evident to those skilled in the art. Specific examples will be given later.

Some specific examples of the synthesis of heavy metal aluminosilicates in accordance with the invention will now be given. From these examples, the general procedure will be clear. It may be noted that if one desires a higher or lower ratio of some particular selected heavy metal to silicon, or a higher or lower ratio of aluminum to silicon in the final product, the relative proportions of these components in the reaction mixture should be adjusted accordingly. The various specific examples illustrate this.

For the sake of an orderly presentation of the examples, the first ones which follow illustrate the practice of the invention where nickel is the sole multivalent lattice cation besides aluminum and silicon. Later ex- 65 amples show other heavy metals and mixtures thereof. Examples A and B are of interest as illustrating the effects of using a relatively insoluble nickel source on the one hand, as in Example A, and of using a relatively soluble nickel source on the other, as in Example B.

In Example A, the nickel occurs predominantly in the dioctahedral phase where it proxies for Al In Example B, the nickel is predominantly in the trioctahedral phase. In both examples, more dioctahedral phase is present than trioctahedral, although more so in the case of Example A.

These examples follow:

EXAMPLE A Forty grams of commercial silicic acid (Fisher), assaying 79% SiO were dispersed in one liter of distilled water. To this dispersion were added, with stirring, 70.8 g of AlCl .6I-I O and 17.6 g NiCI .6I-I O. When solution of these chlorides was complete, 75 ml of aqua ammonia (29% NH were then added to precipitate the hydroxides. The slurry was filtered and washed three times with water by reslurrying and refiltration. The final cake was dispersed in water, 3.0 g NaOl-l (previously dissolved in a small amount of water) added, and the slurry made up to 1 liter.

This slurry was placed in a Type 347 stainless steel Aminco superpressure bomb, with an inside diameter of 2 9/16 inches and an inside depth of 21 inches, equipped with a standard Aminco closure. Heating and stirring were furnished by a standard Aminco heating jacket mounted on a rocker assembly. The jacket temperature was controlled by an off-on device. The bomb was vented, at the boiling point of the contents and without rocking, until the air had been displaced from the vessel. The vent was then closed, rocking started, and the temperature allowed to climb to the control point, 285C. At the end of the scheduled reaction time of 48 hours, heating was discontinued, and the autoclave and contents allowed to cool, with continued rocking. The product slurry, which had a pH of 6, was filtered and the cake redispersed in aqua ammonia and refiltered twice, followed by one such treatment with distilled water. The final filter cake was dried at l 10C. It is estimated that in the final product, the unit cell parameters were w H3 (or -l Ni/u.c.) and x 0.8 (i.e., up to 0.8 A1 IV/u.c.), depending on the distribution of Al between the lV-sites and the charge-balancing hydroxy-aluminum species.

EXAMPLE B 346 g of hydrated alumina, Al O .3H O (Alcoa C 31, 64.9% A1 0 were added with stirring to a polysilicic acid sol which was prepared by passing sodium silicate solution over hydrogenresin. The volume of sol was chosen so as to contain 317 g SiO 8.95 g of NI-I F.HF were then dissolved in this silicaalumina slurry. In a separate vessel, 19.1 g of NiF .4I-I O were dispersed in 63.0 g of an ammonium hydroxide solution assaying 58.8% NI-I OI-I. This ammoniacal slurry was then added to the silica-alumina dispersion, with stirring. If gel formation occurred, sufficient water was added to break the gel so that efficient stirring could continue. The final feed slurry, with a pH 8.5, was charged to a l'-gallon stirred autoclave, heated quickly (1 1% hr.) until pressure line-out at 1240 psig (300C), and maintained at this T,P condition for 3 hours. The product was cooled in the pressure vessel, removed, sheared in a blender to insure homogeneity, and a small quantity dried for analysis. The product slurry had a pH 7.4. The dried sample had a total nickel content of 1.30% (as Ni); the non-exchangeable Ni content was 1.2%.

7 The sample gave an X-ray diffraction pattern typical of 2:1 layer-lattice silicates.

Pd was placed on the clay by adding to 1535 g of product slurry a solution which contained 4.185 g of EXAMPLE E 260 gms of nickel acetate 4-hydrate (NiAc .4H O) were dissolved in 500 ml of deionized water and added,

(NH PdCl dissolved in 125 ml of deionized water. 5 with stirring, to a sufficient quantity of polysilicic acid The slurry was stirred (with mild agitation) overnight at sol (assay: 5.2% SiO to contain 150 gms of SiO With room temperature, and then filtered. The filter cake continued stirring, 7.45 gm of NH F.HF (purity: 96%) was washed twice by redispersion in deionized water and 33.3 gm of aqua ammonia (47% NH OH) were and refiltration. The final filter cake was air-dried at added, in the order given. The resultant mixture was 110C, cooled, and crushed to /20 mesh particles. 10 placed in a l-gal stainless steel stirred autoclave and The final catalyst contained 1.4% Ni and 0.8% Pd. heated quickly (1% hrs) to 300C and 1240 psig. The contents were maintained at these conditions for 4 EXAMPLE C hours. Heating was then discontinued and the product This synthesis was similar to Example B, described slurry cooled in the pressure vessel, removed, and ovabove, except that the proportions of the starting mate- 5 en-dried at 1 10C. rials were altered to yield a clay of approximately 10% While the products in accordance with the invention Ni content. The feed slurry wascomposed of 2890 g of are well crystallized, the actual size of the crystal does polysilicic acid sol (which contained 5.2% SiO 164 g not lend itself readily to characterization by the older Al O .31-1 O, 95.5 g NiF .41-1 O and.42.7 g of NH OH' methods of optical crystallography. Much more precise solution (which contained 47% NH OH). The feed and are the results obtained by x-ray diffraction, and by way product pH were 8.4 and 8.5 respectively. The total of further characterization of the products in accornickel content of the product was 11.1% (as Ni); the dance with the invention, there follow tabulations of non-exchangeable nickel content was 9.9%. Pd was spacings and intensities obtained on a number of prodadded as previously described; the finished catalyst ucts in accordance with the invention. Tables l-IV incontaining 10.1% Ni and 0.8% Pd. clusive show such x-ray diffraction data for two series of products made along the lines indicated in Examples EXAMPLE D B E inclusive.

25 pounds of SiO (as polysilicic acid sol assaying The products tabulated in Table I consist, except at 5.2% SiO were pumped into a feed mix tank equipped the end members, of mixed diand trioctahedral phawith an efficient high-torque stirring system. To this ses. The Ni-free end member is pure dioctahedral; silica sol were added with stirring 27.3 pounds comthe Ni sample is pure trioctahedral. 1n the intermemercial trihydrate of alumina (which assayed 64.9% diate range, the amount of trioctahedral phase in- A1 0 23.5 pounds of nickel acetate.4-hydrate (which creases with the Ni/unit cell. The products summarized cntained 23.7% Ni) previously dissolved in 10 gal H O in Table III are pure trioctahedral. and 1.24 pounds of NH F.HF (purity of 96%) already In the series shown in Tables] and 11, the aluminum in solution in 1 gal H O. With continued stirring, sufficontent was held constant at one and one half atoms cient aqua ammonia was added to bring the slurry pH per unit cell while the nickel content was varied from to 8. This pH adjustment was accomplished with 13 zero to six atoms per unit cell. A summary of the results pounds of aqua ammonia, which contained 48% obtained is given in Table I, with a more detailed tabu- N1-1 OH. The final volume of slurry was about 75 gal. lation in Table 11, It will be understood that the first After approximately 10 hr. of agitation, the feed member of this series, in which no nickel is present at slurry was pumped into a 100 gal jacketed autoclave, all is outside of the scope of the invention; the results heated by electric heaters immersed in Dowtherm. The are shown merely for comparative purposes. autoclave was sealed and heating started. After 12hr- 1n the series for which results are given in Tables 111 min., temperature lined out at 300C and apressure 45 and IV, the nickel content was held constant at six of 1240 psig. The contents were maintained at these atoms per unit cell, while the tetrahedral aluminum was conditions for 4 hrs at which time drawdown through a varied from zero to two atoms per unit cell. Here again, quench condenser and expansion valve was started. the first member of the series, containing no aluminum, Total time for discharge was 1 hr. A small sample was is outside of the scope of this invention and the results dried, examined and found to be a 2:1 layer-lattice are included in the tabulation for comparative puraluminosilicate which contained 9.6% Ni. A portion of poses. Table 111 is a summary, and Table IV shows the the product was retained as slurry for after-treatment results in detail for each member of the series. by Pd impregnation as previously described.

TABLE 1 SUMMARY Ni VARIABLE, x=1.5 d,A lndex* Ni/u.c. 0 H8 1 2. 3 4 5 v 6 001 10.6 11.8 11.3 11.3 13.0 13 4 13.4 13.6 002 5.18 5.68 5.34 5.24 003 3.41 3.26 3.37 3.34 004 3.30 3.26 3.24 3 29 hkO05 2.061 2.065

hkl 1.502) 1.502) 1.500)

TABLE l-continued SUMMARY Ni VARIABLE, x=l.5

1ndex* Ni/u.c.:o [/8 1 2 3 4 5 6 131(Prob.) 2.453 2.45 2.453 2.42 2.466 2.47 2.51

Significant peaks only. See detailed tables for intensity data. Basal sequence may involve mixed layering. If so, indices would be mixed; c.g. 003/004. "Doublet consisting of diand trioctaheclral components.

"Probably intcrcalatcd acetate TABLE 11 Ni VARIABLE, x 1.5 (BASED ON STARTING COMPOSITION) Ni=l/8 u.c.

Probable d,A lndex Height, mm Comment 1 1.8 001/001 172 Strong, Symmetrical 5.68 002/002(?) 18 Weak, Symmetrical 4.46 1 1',02 148 5.5 mm,w/2* Strong, Asymmetrical 3.26 003/004 48 Symmetrical 2.56 13,20 65 Asymmetrical (band,2.3 l-2.62) 2.45 hk 36 Shoulder 2.065 00 l8 Symmetrical 1.687 31,15,24 2O Asymmetrical 1.492 06 42 12mm, w at h/2** Slightly Assymetrical *w/2=half-width at baseline. For asymmetrical peak, smaller distance **w at hl2=width at half-height Ni=1/u.c.

Probable d,A lndex Height, mm Comment 1 1.32 A 001/001 140 Strong, well defined 5.34 002/002 1 1 Weak, Symmetrical 4.50 1 1,02 147 7.5 mm w/2 Asymmetrical, Sharp 3.37 003/004 47 Symmetrical, broad 2.583 13,20 102 Asymmetrical, Mod. sharp 2.453 hk 56 Symmetrical 1.699 3 l;15;24 17 Asymmetrical, broad 1.517} 06 22 Doublet 1.517 is 1.502 48 a shoulder on low-angle side of 1.502

Ni 2/u.c.

Probable d,A lndex Height, mm Comment 1 1.32 001/001 135 Not well-defined 5.24 002/002 6 Symmetrical 4.48 1 1,02 122 6mm w/2 Strong, sharp, asymmetrical 3.34 003/004 Symmetrical, broad 2.57 1320 93 Asymmetrical, Mod sharp 2.42 hk Asymmetrical 1.67 3l;15;24 13 1.522} 06 35 {Doublet about equal 1.502 35 height; trioct. dioct.

Ni 3/u.c.

Probable d,A Index Height, mm Comment 13.0 001/001 190 May have intercalated acetate 4.48 l l;02 11m w/2 Asymmetrical 3.30 003/004 40 Broad, symmetrical 2.576 13;20 96 Mod. sharp, asymmetrical 2.466 hk 61 lll-defined 1.691 31;15;24 15 Broad 1.520} 06 53 Doublet 1.500 A a shoulder 1.500 on high angle side of 1.520

trioct. Uncertain due to complications due to mixed layers. Ni=4/u.c.

Probable d,A lndex Height, mm Component 13.4 A 001/001 201 Ill-defined may have intercalated acetate 4.50 1 1;02 56 14mm w/2 Asymmetrical 3.26 00 38 Broad, symmetrical 2 .5 8 13 ,20 86 Asymmetrical 2.47 hk 58 Broad shoulder on 2.58 1.522 06 67 Asymmetrical tailing toward high angle side Ni=5/u.c.

Probable d,A lndex Height, mm Comment 13.4 001 200 mm Uncertain height not well defined Ni VARIABLE, x 1.5 (BASED ON STARTING COMPOSITION) Ni=1l8 u.c.

Probable d,A Index Height, mm Comment 4.55 1l;02 58 mm 9 mm w/2 Asymmetrical 3.24 45 a Symmetrical 2.61 13;20 9O Asymmetrical band head band extends 2.64 1.97 1.524 06 87 Asymmetrical tails toward high angle side *Uncertain due to complications due to mixed layers.

Ni 6/u.c.

Probable d,A lndex Height, mm Comment 13.6 001* 192 Poorly defined may be intercalated acetate 4.54 11;02 59 9 mm w/2 Asymmetrical 3.29 004* 40 Very broad, symmetrical 2.58 13;20 83 Broad, band-head of band extending from 2.64 1.97 A 2.51 hk 84 Part of above band 1.522 06 98 14mm,width Mod. sharp asymm. tailing at h/2 to high angle side *Uncertain due to complications due to mixed layers.

TABLE III-continued TABLE III SUMMARY SUMMARY Ni 6, x VARIABLE Ni 6, x VARIABLE AL"u.c. AL "u.c. lndex 1/2 1 1.5 2 Index* 0 1/2 1 1.5 2

001 9.6 11.6 13.4 13 6 06 1.522 1.522 1.524 1.522 1.526 002 hkl 003 3.145 131(prob) 2.51 2.51 2.51 004 3.25 3.32 3.29 3.42 005 Significant peaks only. See detailed tables for intensity data. Basal Sequence may l'lk involve mixed-layering. If so, indices would be mixed; e.g., 003/004. Also, possible 1 1;()2 4,55 455 456 454 453 intercalation. of acetate may affect 00. 13;20 2.62 2.59 2,58 2 62 35 This particular sample, when oriented and glycol treated, gave an 001 of 17.7 A. 22;04 2.27

TABLE IV x 2.0 (expectation value) Ni 6, X VARIABLE asymmetric.

NOTE: 001-is not defined; slight trace of kaolinite-like phase at 7.08 A.

t x 1.5 (expectation value) Probable d,A Index Height, mm Comment 13.6 001 192 Poorly defined. 4.54 11;02 59' 9 mm, w/2 Asymmetrical 3.29 004* Very broad, symmetrical 2.58 1320 83 Broad; part of band 2.51 hk 84 extending from 2.64 1.97 A 1.522 06 98.5 14 mm, w at h/2 Moderately sharp; slightly asymmetric *Uncertain due to complications due to mixed layers. x 1.0 (expectation value) Probable d,A lndex Height, mm Comment 13.4 001 191 Well-defined on oriented slide;

poorly-defined on random slide. (expanded to 17.7 A w/glycol treatment) 456 1; 61 11 mm, w/2 Asymmetrical 3.32 004* 41 Very broad, symmetrical 2.59 13;20 83 Asymmetrical band extending from 2.661 1.97 1.524 06 14 mm, w at h/2 Moderately sharp; slightly asymmetric.

Ni 6, X VARIABLE x 2.0 (expectation value) Probable d,A Index Height, mm Comment x 0.5 (expectation value) Probable d,A Index Height, mm Comment 1 1.6 001/001 224 Strong, well-defined.

4.55 I I;02 81 7 mm, w/2 Asymmetrical 3.25 003/004 57 Broad, symmetrical 2.62 13;20 hk 84 Band-head listed. Band extends 2.64 1.97 A, asymmetrical. 1.522 06 114 9 mm, w at h/2 Sharp; slightly asymmetric Probable d,A Index Height, mm Comment 9.6 001 227 V. strong, well-defined, symm. 4.55 1l;02 97 mm 8 mm, w/2 Asymmetrical 3.145 003 93 Moderately sharp, symm.

2.51 l3;20 106 Band (strongly asymm.)

1.522 06 120 8 mm, w at h/2 Sharp, slightly asymmetric Uncertain due to complications due to mixed layers.

Returning now to Example A, as already noted, and values of 3w of from 0 to 6. For this particular system,

as may be seen from the details set forth in the example, the nickel occurs predominantly in the dioctahedral phase. A tabulation of x-ray data for the product of Example A is set forth in Table 5, which follows.

any amount of nickel added (within the compositional limits) crystallizes as a trioctahedral nickel silicate which may or may not contain 4-coordinated Al. Thus, in this system, any mixture of NiO and A1 0 which TABLE V w 1/3 (ca. 1 Ni per unit cell) and x=0.8 (expectation value) Probable d,A Index Height, mm Comment 12.0 001/001 100 Ill-defined, symmetrical 4.45 11;02 134 8 mm, w/2 Sharp, asymmetrical 3.16 003/004 Broad, slightly asymmetrical 2.55 I3;20 64 Broad, assymetrical 1.686 31;l5;24 15 Broad, asymmetrical 1.491 06 37 18 mm, w at h/2 Asymmetrical on low-andle side indicating a small amount low-angle trioctahedral component From size considerations alone Ni is expected to occupy octahedral sites and to be excluded from tetrahedral sites in the layer structure, or to occupy chargebalancing sites either as Ni or as a hydroxy-nickel species. Al, however, can occupy octahedral, tetrahedral, or charge-balancing sites; in the latter case, a hydroxy-aluminum species is to be expected. The diffraction data in the previous tables show 06 reflections typical of mixed dioctahedral/trioctahedral minerals. Furthermore, the trioctahedral 06 1 .505A) peak height increases, and the dioctahedral 06 l.505A) peak height decreases, as the overall average Ni per unit cell varies over the range 0 to 6. In addition, reference is made to the attached drawing wherein the intensity of the trioctahedral 06 reflection, corrected for change in the mass absorption coefficient as Ni increases and Al decreases, is plotted as a function of the expected overall average level of Ni, i.e. the expected overall average Ni per unit cell based on feed composition. In the drawing, h(O6 is the 06 peak height in chart units;p./p is the mass absorption coefficient and the Ni/unit cell is equal to 3w as defined in the formula given at the beginning of this specification. Note that the intensity is a linear function of Ni/u.c. and that the line extrapolates to zero intensity at zero nickel level. The line w in FIG. 1 is the best fit for the experimental points which represent values ofx from 0.5 to 1.45 and contains less than the amount of Ni required for 6 Ni/u.c. will form mixed dioctahedral-trioctahedral phases.

As already stated, one of the principal fields of utility for products made in accordance with the invention is in the field of hydrocarbon conversion, such as for example catalytic cracking. In a series of cracking experiments in which cumene was passed over samples of the inventive preparations at 350C., the results set forth in Table 6 were obtained. In this tabulation, the first 12 entries represent cumene cracking results on various preparations made along the general lines of Examples B-E inclusive. For each sample, the values of w and of x are given, based upon the structural formulation presented earlier in this specification. The last entry in Table 6 is for a preparation made in accordance with U.S. Pat. No. 2,658,875, cited hereinabove, and which results in a lattice which is chargebalanced, as already noted, and for which accordingly x equals zero. This preparation is termed nickel montmorillonite in the patent, although I consider that a more exact term is nickel tale.

The first column of figures in Table 6 gives the percent conversion, which is the volume percent conversion of cumene to all products corrected to mass balance. The latter is the ratio of the mass of total products recovered to the mass of cumene fed, multi? plied by 100. The experimental figures are given in the last column of Table 6. I

The catalytic apparatus used was essentially a micro device, two microliters of cumene being slugged at a flow rate of an inert carrier gas of 0.5 cubic centimeters per second. The table shows two duplicate runs, from which the excellent reproducibility of the results may be judged.

This cracking test essentially determines the ability of the catalyst to crack the aliphatic side chain from the benzene ring. That the samples in accordance with the invention were highly successful in doing this is clear from the table. Also worthy of note is the remarkably low figure for the nickel talc shown in the last line of the table; this substance had no cumene cracking activity whatsoever at the temperature employed in the test.

TABLE VI Cumene Cracking Conversion Mass Balance Description of Sample The foregoing examples have illustrated the employment of nickel in the inventive aluminosilicates. Next, a group of examples will follow showing other heavy metals used in accordance with the invention.

EXAMPLE F 40 gms silicic acid (assaying 79% SiO were dispersed in 1 liter of H 0. With continued stirring, 70.8 g A1Cl 6H O and 17.6 g cobalt chloride, CoCl 6H O, were dissolved in the silica slurry. At this point 75 m1 of aqua ammonia (29% NH;,) were added to precipitate the mixed hydrousoxides. The slurry was filtered and washed by redispersion and filtration through a total of 1 three wash cycles. The filter cake was dispersed in water, 3.0 g NaOl-l dissolved in the dispersion, and the total volumemade up to.1 liter. The 'pH at this point was 9.5..

The slurry'was placed in a super-pressure bomb and.

heated, with rocking, at 285C. for 2 days. The pressure was 1040 psi. After cooling, the bomb was opened and the product slurry filtered. The filter cake was washed (by redispersion and refiltration) twice with aqueous ammonia and once with water, and then dried in an oven at 1 109C.

, EXAMPLE 0 (29% NHg). This final slurry was filtered and washed with water by redispersion and filtration through three I cycles. The filter cake was redispersed in 11 0, 1.80 g '1 NaOH dissolved in the mixture, and the total volume broughtto 1 liter by adding additional water. The slurry was charged" to a super-pressure bomb and treated, with rocking, at 285C. and 1040 psi for 2 days. After cooling, the bomb contents were filtered and then washed, by redispersion and refiltration, twice with aqua ammonia and once with water. The final filter cake was dried in an oven at 1 10C.

EXAMPLE H 40 g of ball-milled silicic acid (79% SiO were dispersed in water and, with continued stirring, 70.8 g of AlCl 611 0 and 19.72 g chromium chloride, CrCl 61-1 0, were dissolved in the silica slurry. At this point, m1 of aqua ammonia (29% N11 were added to precipitate the hydrous oxides. This mixture of silica, chromia, and alumina was filtered and washed with water by redispersion and refiltration, through three cycles. The final filter cake was dispersed in water, 2.36 g of NaOH dissolved in the mixture, and the volume made up to 1 liter with additional water. The slurry was charged to the Aminco super-pressure bomb and treated at 285C. with 1040 psi for 48 hours. After cooling, the product slurry was filtered and the cake washed twice with aqua ammonia and once with water, by the previously described redispersion technique. The final filter cake was dried in an oven at 110C.

EXAMPLE I In a manner similar to Example H, a product was prepared from 40 g ball-milled silicic acid (79% SiO 70.8 g A1Cl 61-1 0; 20.19 g ferric chloride, FeCl 61-1 0; 75 ml aqua ammonia (29% NH;,); 2.36 g NaOI-I;

and sufficient water and additional ammonia to carry out the various operations.

EXAMPLE I In a manner similar to Example F, a product was prepared from 40 g of ball-milled silicic acid (79% SiO 70.8 g AlCl 61-1 0; 7.52 g cupric fluoride, CuF 75 ml aqua ammonia (29% N11 2.36 g NaOl-l; and sufficient water and additional ammonia to complete the various operations.

EXAMPLE K 28.5 g SiO (as 500 g polysilicic acid gel) were dispersed in 200 ml water and 21.6 g A1 0 31-1 0 (commercial Alcoa C-33 alumina trihydrate) added, with continued stirring, to give a silica-alumina slurry. 12.1 g zinc silicofluoride, ZnSiF 611 0, were dissolved in ml water and added to the above slurry, again with vigorous stirring. Finally, 1.03 g NI-1 F were dissolved in 2.5 ml H O andadded to the mixture, also with stirring. The small beaker containing the NI-I F solution was rinsed into the mixture with additional water. The volume of this final mixture was brought to 1000 ml with additionalwater; the pH at this point was 6. 900 ml of the mixture were charged to the super-pressure bomb and treated at 300C. and 1240 psig for 2 days. After cooling th'eproduct was filtered, washed with water; and dried in an oven at C.

. EXAMPLE L 500 g of polysilicic acid gel which contained 28.5 g Si0 were dispersed in 250 ml of water, together with 21.8 g of A1 0 3H O, (commercial'Alcoa C-33 alumina trihydrate). 1n aseparate vessel, 1.03 g Nl-I F, 2.5 ml aqua ammonia (29% NH;,) and 3.53 g ammonium 17 paratungstate were dissolved in 450 ml of water with vigorous stirring. The paratungstate was slow to dissolve and as this solution was added to the silicaalumina slurry, with stirring, it was noted that some The foregoing examples all correspond to the series:

7 SiO (5 a) A (OI-1);; oz MgO wherein a varies from zero to 4, as given in the above tabulation.

undissolved paratungstate was present. The total vol- 5 The number of Products ected from the foregoing ume was brought to 1350 ml with additional water (at examples w for catalytic cracking e this point the pH 9), and 1000 ml were charged to the The following tabulation shows the results of dimethylsuper-pressure bomb and treated at 300C. and 1240 butane crackmg at 525C psig for 2 days. After cooling, the product slurry pl-I TABLE VII was 7.7. The slurry was filtered, washed with water, and 10 Com B surface Area the filter cake dried in an oven at l 10C. Example Metal Kcavflnole mr/gm EXAMPLE M A Ni 187 F Co 30 22 156 In a manner similar to Example K, a mineral was H Cr 214 synthesiaed from: 500 g polysilicic acid gel (containing 1'2 28.5 g S10 10.5 g magnesium sillcofluortde, MgSIF N Al 88 18.2 96.5 1.03 g NH F; 2.5 ml NI-I OH; and sufficient water to 2 M :5 bring final volume to 1300 ml. 1000 ml were charged to Q g 1 43 105 the bomb and treated hydrothermally at 300C., for 2 R Mg 45 174 y The product was filtered: washed water, and Extremely active catalyst. Products contained only C,CH H Nature ofproducts dried in an oven at l 10C, put run outside the scope of the DMB method.

Note: Catalyst pretreatment did not include steam deactivation. EXAMPLES N, O, P, Q, R

These five examples constitute a series of increasing The Succeeding tabulation Shows the results of magnesium content. The manner of preparation was lane cracking tests at TABLE VIII Conv. Gaso. Vol H2, liters STP gm Coke Example Metal 500C. Conv. per gm Cetane Cracked gm Cetane Cracked A Ni 79.5 0.202 0.410 0.282

J Cu 40.6 0.436 0.14

N Al 65 .9 0.517 0.0055 0.0094

0 Mg 68.4 0.570 0.0500 P Mg 34.9 0.896 Q Mg 3.8 1.0 R Mg 69.4 0.527

the same for all fiveexamples, except for the quant ties EXAMPLES S T U, V, w of aluminum chloride, sodium chloride, and sodium hydroxide The procedure was as follows; These five examples constitute a series Of similar T 40 g f diatomaceous earth (C li 521 dispersed preparationsin which cobalt and mixtures of nickel and in one liter of distilled water, there were added, with Cobalt were Included the Preparations- The gehelal Stirring, A g f AlC]3 1-1 0 and 3 g of Mgclz 6 H2O procedure was the same for all examples in this group Aft l i was complete, 150 1 f aqua ammonia and consisted of mixing the starting materials specified 29% M4, were added, with continued stirring, to below in t p p9 g mixing i g v, and precipitate the hydrous oxides. The resultant SiO Al charging lhte a sllver hhed, 15 ml p y Stainless Slurry was filt d and washed until f f steel autoclave. This was sealed and heated in afurnace Cl ion, redispersed in H O to a total volume of 1 liter, at 350C. for 24 hours- At the end of this P the and C g f NaOH, dissolved in a minimum amount f autoclave was removed, quenched in cold water, and water, added with stirring. This final mixture was the contents removed- The Product Slurry was mixed charged to an Aminco uperpressure bomb and heated deionized water agitation and then filtered with rocking, at 2 5c f 2 days Aft cooling, the and washed until free of chloride ion. The filter cake bomb was opened and the product slurry filtered. The was dl'led ig g and Studied by filter cake was washed (by redispersion and refiltray and h' h q tion) twice with aqueous ammonia and once with water The following materials were used: and then dried in an oven at l 10C. A ml of 2-213 fermall Ceclz Solution,

The various values of A, B, and C follow: 60 B ml of 3-O85 F Niclz Solution,

C m1 of 2.390 AlCl solution, Example A g B g Q g a, g D ml of 10.09 F (or N) NaOH solution,

(or, in some cases, E ml of 10.97 N NaOH solution), g 3% g 3 f F gms of Fisher silicic acid sio 0.635 H 0 and P 69.0 38.7 3.8 2 G ml deionized water 0 46.0 58.0 3.8 3 *Formula weight/liter of solution; Formality x milliliters millimoles; R 23.0 77.4 3.8 4 all aqueous solutions made with deionized water.

The various values of A, B, C, D, E, F, and G for the examples are given below:

Example A, ml B, ml C. ml D, ml E, ml F, g G, ml 1 s 9.04 16.76 17.2 4.76 8.4 T 27.12 8.4 19.9 4.28 1.6 U 1.13 0.80 16.2 12.2 5.11 16.8 v 4.52 3.22 16.76 17.2 5.23 5.9 w 13.6 9.65 8.4 18.2 4.71 1.6

Structural investigations by X-ray diffraction and infrared spectroscopy gave the following results for the products obtained:

ion. Adequacy of the analysis is indicated if this corrected total lies between 99.5 and 100.5%. The analysis is recalculated as charge equivalents (i.e., cation equiv- TABLE lX 001 spacing, O6 spacing Wt 06 Sp. Wt. Ex. Colu.c. N1/u.c. x A trioct., A 'Fac. dioct.,A Fac.

S 2 nil 4/3 14.5 1.531 390 1.495 C 320 T 6 nil 2 14.7 1.538 1090 n.p.* U 0.25 0.25 l/3 11.2 mg. 1.488 680 V 1 1 4/3 12.6 1.5 6 410 1.489 260 W 3 3 2 13.2 1.531 1220 up 'n.p.: not present.

In Table IX, the second and third columns give the number of atoms of cobalt and nickel respectively per unit cell. The value of x given refers to the general structural formula given near the beginning of this specification. The 001 spacing was determined by X-ray diffraction, and the trioctahedral and dioctahedral 06 spacings were likewise thus determined. The

weight factor expresses the relative preponderance of being examined should be substantially free of accessory phases.

It is then necessary to obtain a total anaylsis of the sample, expressed as the oxides of the cations in their alents x cation charge), normalized to charges per 44 charges (the negative charge per unit cell of the oxygen-hydroxyl framework of the 2:1 layer silicates) and finally expressed as cations per unit cell (e.g., the silicon charges per 44 charges divided by thecharge of the silicon cation). These cations are then distributed over the tetrahedral and octahedral layers in accord with the tabulated lists of cations falling into the categories G, Y, Q, and R. In this way the values of the various subscripts in the general formula can be obtained. Examples of this technique, a statement of the rules for cation distribution, and a discussion of the uncertainties involved and the meaning of the results can be found in Kelly, W. P., Interpretation of chemical analyses of clays, Clays and Clay Technology, Bulletin 169 of the California Division of Mines (1955), pp. 92-94; and Osthaus, B. B., Interpretation of chemical analyses of montmorillonite, same reference, pp. 95-100.

An illustrative example follows. This particular example has been selected to include the complexities arising from mixed diand trioctahedral phases, mixed 1:1 and 3:2 substitution octahedrally, and mixed 4- and 6-fold coordinated aluminum ion.

Charges Cation Charge 44 Cations Analysis Equiv. Equiv. Charges U.C. Distribution SiO, 50.59 0.842 3.37 27.59 6.90 Tet: Si,6.90 A1 0 23.33 0.458 1.37 11.25 3.75 Al,1.10. 1.10- MD 16.86 0.226 0.451 3.70 1.85 Oct: 'A1,2.65 I (NH ),O 4.61 0.177 0.177 1.45 1.45 Ni,1.85 0.35-

F 2.09 0.1 10 I 1.45 H 0 3.41 lnter- 100.89 5.369 43.99 layer: NH 1.45 1.45+

Corr. Total 100.01

From the tabulated calculation, x in the general formula is 1.10, 3w is 1.85, and ew=42.65 1.35, so that 2 2.19. The value of f can be obtained by noting that F/Si=f/(8x)=0.131. Since x=1.10,f-0.90. The coefficient, d, of the amount of exchange ion (NI-l is 1.45.

Therefore, the average formula for this example is LlO 21) )3.1 03] 4' Comparison of the inventive ranges of x, e, w,f, and d and the ions which can fill the roles of G, Y, Q, R, and.

21 C with the results shown above demonstrates that the example falls within the scope of the invention.

An alternate method of calculationis based on the use of ionic ratios. However, the method is still dependent on the aluminum distribution between 4- and 6-fold states. If we define Si/Al R ==(8 x)/(4 ew x); Si/Ni=R =(8 x)/3w; Al' /Al '=R and F/Si R f/(8 x), it can be shown that e (4R x)/w R3 d (if exchange cation is monovalent) =x (e 2)3w Once x is obtained from the ratios and eq (1), w can be calculated according to eq. (2), e from eq (3) with x and w; and finally d from eq. (4). From the analysis given, R 1.84; R 3.73; and R 0.131. From the distribution given, R 0.416. Thus, x 1.10; w 0.617, e=2.19, and d 1.45 from equations 1 through 4, in good agreement with the values obtained by the distribution procedure. The value of f can be recovered from R, as shown above. This calculation is presented simply to show the validity of equations 1 through 4. Given such validity, any analytical method or combination of methods that provides accurate values of the required ratios will give the correct values of x, w, e, and d.

From the foregoing examples, it is apparent that a general method of producing the laminar 2:1 layer lattice aluminosilicate mineral of this invention can be described in the following manner. To a dispersion of amorphous silica in water is added, with stirring, suit able sources of the ions G, Y, Q, and R, (note that silicon is the predominant part of Q).

Such sources are the hydrous oxides and simple inorganic and organic salts of the ions listed in the tables of ionic radii, which were presented hereinabove. If a salt is used, it is convenient, but not necessary, to choose anions which either enter lattice positions (for example, fluoride or silicofluoride) or are readily removed from the product by calcination (for example, acetate and nitrate). Alternatively, anions may be selected which result in soluble by-products which can be removed from the feed slurry or alternatively from the product by filtration and washing. However, the filtration rates of layer aluminosilicates are low and largescale production filtration of the product is best avoided.

Once the mixture of silica and G, Y, Q, and R is obtained, within the compositional limits stated hereinabove, the appropriate amount of charge-balancing cation C is added, conveniently as the hydroxide or fluoride or mixtures of both. As stated hereinabove, C may be selected from the group consisting of alkali metal, alkaline earth metal, heavy metal, heavy metal partial hydroxy, ammonium, substituted ammonium, substituted phosphonium, and the like cations and mixtures thereof. lt is preferred that C be ammonium.

This final feed mixture is then charged to a pressure vessel and heated under at least autogenous pressure at a temperature generally in the range 250C to 350C. In general, the time for crystallization of the product decreases with increase in temperature. However, the pressure increases with temperature and the higher temperatures require massive reaction vessels. A convenient temperature is 300C, which in an aqueous system results in a pressure of 1240 psig. At the end of the crystallization time, the product slurry can be cooled by any convenient means (for example, discharge through a quench condenser and a throttling valve to atmospheric pressure). The product can be recovered by direct drying of the slurry if the unwanted anions present are thermally decomposable, or by filtration, washing, and drying if these anions are not thermally decomposable but are present as soluble by-products. The product can then be further treated by whatever processing is required by the intended end use. For example, the product can be exchanged to the ammonium form, dried, at for example C to C, and then if desired calcined, for example, at 400C to 700C. It then is suitable for many catalytic operations, such as hydrocarbon cracking. Of course, if the temperature during the catalytic procedure is high, for example within the exemplary calcination range just given, then calcination need not be a separate step, as it occurs automatically. For other catalytic operations, the ammonium exchange, the drying, or the calcining, or all three, may be variously omitted.

It will be understood that while 1 have explained the invention with the aid of numerous specific examples, nevertheless considerable variation is possible in choice of raw materials, proportions, processing conditions, and the like, within the broad scope of the invention as set forth in the claims which follow:

Having described the invention, I claim:

1. The process of cracking hydrocarbons which comprises'contacting a hydrocarbon feedstock with a catalyst which is a laminar 2:1 layer-lattice aluminosilicate mineral possessing an inherent negative charge balanced by cations exterior to said lattice and corresponding to the following formula for a given embodiwhere 2 s e s3 0.01 s w s 2 0.02 s eiv$4 0.05 s x $2.0

wherein said first bracket represents said layer-lattice unit cell formulation and said second bracket represents said charge balancing cations; and wherein G is at least 0.8 mol fraction aluminum ion, the remainder consisting of trivalent metal cations having an ionic radius not to exceed 0.75 A; Y is selected from the class consisting of divalent metallic ions having an ionic radius not to exceed 0.75 A and mixtures thereof;

Q is at least 0.95 mol fraction silicon ions, the remainder consisting of tetravalent ions having an ionic radius not to exceed 0.64 A;

R is selected from the group consisting of trivalent ions having an ionic radius not to exceed 0.64 A and mixtures thereof; and

C is at least one charge-balancing cation, with y being its valence and d being the number of such cations C where:

dy x 3 (e2)w, said contacting being at a temperature high enough to bring about cracking. and thereafter recovering the products resulting from said cracking.

2. The process-of cracking hydrocarbons in accordance with claim 1, wherein said Y is nickel,

3. The process of cracking hydrocarbons in accordance with claim 1 wherein said second bracket has the composition 4. The process of cracking hydrocarbons in accordance with claim 1 wherein prior to said cracking said mineral has been placed into its ammonium exchange form and'thereafter calcined.

5. The process of cracking hydrocarbons in accordance with claim 4 wherein saidcalcination takes place at a temperature within the range of about 400 to about 700"C.

Patent Citations
Cited PatentFiling datePublication dateApplicantTitle
US1759919 *Dec 9, 1927May 27, 1930Singer FelixArtificial plagioclase compound
US3252889 *Jul 16, 1963May 24, 1966Gulf Research Development CoCracking catalyst and process of cracking
US3803026 *May 19, 1970Apr 9, 1974Chevron ResHydrothermal method for manufacturing a novel catalytic material,catalysts containing said material,and processes using said catalysts
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Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US4022684 *Apr 26, 1976May 10, 1977Gulf Research & Development CompanyHydrocarbon conversion process using a Ni and/or CO substituted synthetic aluminosilicate catalyst
US4065380 *Oct 17, 1975Dec 27, 1977Gulf Research & Development CompanyHydrodenitrification using a tungsten containing Ni-SMM composite catalyst
US4138326 *Aug 23, 1977Feb 6, 1979Gulf Research & DevelopmentHydrotreating process and catalyst
EP0145061A2 *Nov 15, 1984Jun 19, 1985Shell Internationale Research Maatschappij B.V.Silica-clay complexes
EP0145061A3 *Nov 15, 1984Jul 10, 1985Shell Internationale Research Maatschappij B.V.Silica-clay complexes
Classifications
U.S. Classification208/120.15, 208/120.35, 208/120.25, 502/74
International ClassificationB01J21/12, C01B33/42, C10G11/04, C07C4/18, C07C4/06
Cooperative ClassificationC01B33/42, C10G11/04, C07C4/06, C07C4/18, C07C2521/12, B01J21/12
European ClassificationC07C4/18, C10G11/04, C07C4/06, B01J21/12, C01B33/42
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